微孔聚丙烯中空纤维膜的研究与开发

综述了聚丙烯中空纤维膜的研究与开发状况 ,包括制备原理、过程、影响因素及应用开发状况。重点综述了聚丙烯中空纤维膜的制备及结构性能     

聚丙烯中空纤维膜的微孔结构的控制

通过熔纺／冷拉伸法制备了微孔聚丙烯中空纤维膜。研究了工艺条件对微孔聚丙烯中空纤维膜的微孔结构与性能的影响。结果表明：随着纺丝温度的下降或熔体拉伸比的提高，最大可几孔径及孔隙率增大；熔纺中冷却风速提高，最大可几孔径及孔隙率较大；温度低于110℃时，热处理对最大可几孔径及孔隙率的影响较小，在120－130℃时，随着热处理温度的增加，最大孔径及孔隙率有明显增加的趋势；随着初纺中空纤维拉伸倍数的增加，孔隙率先增加而后下降。     

硬弹性聚丙烯的排状堆积片晶

用广角X射线衍射、小角X光散射等手段对硬弹性聚丙烯中排状堆积片晶的形成及结构进行了研究。结果表明,应力场下聚丙烯熔体结晶,得到的硬弹性聚丙烯具有垂直于挤出方向而又平行堆积的片晶结构(即排状堆积片晶)。熔融温度越高,排状堆积片晶所需的熔体拉伸比越高。而随着熔体所受拉伸比的增加,片晶厚度有所增加。随着熔融温度升高,片晶厚度下降。热处理温度在110-120℃之间,片晶厚度随热处理温度升高明显增加。     

微孔聚丙烯中空纤维膜熔纺过程的动力学及结构发展的数值模拟——(1)数学模型

利用力平衡、质量守恒、能量守恒等原理推导了一组一阶非线性常微分方程组，用于描述聚丙烯中空纤维膜原纤熔纺过程的动力学及结构的发展。     

熔融-拉伸法制备亲水聚丙烯/聚乙烯醇缩丁醛中空纤维膜

以聚丙烯(PP)为基材,聚乙烯醇缩丁醛(PVB)为亲水改性剂,聚丙烯接枝马来酸酐(PP-g-MAH)为增容剂,通过熔融-拉伸法(MS-S)制备亲水PP/PVB中空纤维膜.采用差示扫描量热(DSC)和水接触角(WCA)测试考察了PVB添加量对PP/PVB共混物结晶行为及亲水性的影响;采用广角X射线衍射(WAXD)和小角X射线散射(SAXS)研究了PP/PVB中空纤维热处理后片晶微观结构;采用场发射扫描电镜(FESEM)观察了PP/PVB中空纤维膜内表面孔结构的变化,测试了PP/PVB中空纤维膜的孔隙率及纯水通量.研究结果表明,随着PVB含量的增加,PP/PVB共混物的WCA从103°降低到76°,表明PP/PVB共混物亲水性得到明显改善.同时,PVB可以起到异相成核作用,但由于MAH与PVB发生键合作用,过量添加PVB会阻碍PP分子链段运动,导致晶体结构不完善,这与WAXD和SAXS分析结果相同.PP/PVB2.5(PVB质量分数为2.5%)中空纤维膜热处理后结晶度、片晶取向度、厚度及Shish-kebab结构完善度均高于纯PP样品.对应膜孔隙率为66%,纯水通量达到320 L/(m2·h),比纯PP膜提高了76.8%.     

添加PVP和涂覆聚合物对PAN基中空纤维炭膜性能的影响

研究了用ＰＡＮ基中空纤维膜为基质制备气体分离用中空纤维炭膜的过程。考察了添加剂ＰＶＰ对炭膜的Ｈ２，Ｎ２气体渗透速率，分离系九和柔韧性的影响。同时，研究了用丙烯腈共聚物对中空纤维炭膜涂覆改性后Ｈ２，Ｎ２气体的渗透速率和分离系数。     

Armos/聚砜共混中空纤维基膜及其纳滤复合膜的制备与性能研究

中空纤维膜因其体积装填密度高、占地面积小、成本相对低等优点备受关注。本文通过将Armos聚合液与聚砜(PSf)共混，经干-湿法纺丝制备了Armos/PSf共混中空纤维超滤膜，研究表明：Armos均匀分散在中空纤维膜中，中空纤维膜断面呈现疏松的多孔结构，随着Armos共混含量的增加，膜的亲水性和纯水通量均提高，但对PEG-20000截留率下降明显。以Armos/PSf共混中空纤维膜为基膜，通过界面聚合制备了中空纤维复合纳滤膜，优化的制备条件为：基膜中Armos的共混含量为4%、水相单体浓度为3%、油相单体浓度为0.15%时，制得的中空纤维复合纳滤膜性能最佳，其通量为8.40L/(m²·h)，对MgSO₄的截留率为88%。     

同质编织管增强型聚丙烯腈中空纤维膜研究

利用二维编织技术将聚丙烯腈(PAN)纤维编织成中空编织管,以聚丙烯腈为成膜聚合物,以聚乙二醇为成孔剂,配制铸膜液,采用同心圆纺丝法制备同质编织管增强型聚丙烯腈中空纤维膜.研究结果表明,所得同质编织管增强型聚丙烯腈中空纤维膜的表面分离层具有类似于非对称膜的结构,铸膜液可渗入编织管纤维束中;随着编织管编织节距的增大,同质编织管增强型聚丙烯腈中空纤维膜表面分离层厚度减小,同时膜的平均孔径增大,膜的纯水通量随之增大;铸膜液渗入编织管纤维束的现象未影响膜的通透性能;编织管的断裂强度最大可达100 MPa以上.通过水浴振荡、超声波水浴振荡及等力拉伸3种方法测试了同质编织管增强型中空纤维膜和异质编织管增强型中空纤维膜中编织管与表面分离层之间的界面结合性能,结果表明前者的界面结合性能优于后者.     

PAN基中空纤维炭膜炭化条件的研究

研究了以ＰＡＮ其中空纤维膜为基质制备中空纤维央膜的过程。考察了ＰＡＮ厚膜的预氧化和炭化条件对中空纤维炭膜Ｈ２，Ｎ２气体渗透性和选择性的影响。结果表明，预氧化温度和时间对Ｈ２，Ｎ２气体的渗透速率有一定影响；     

高分子量级分含量对熔体挤出拉伸法制备聚丙烯微孔膜的影响

通过熔体挤出拉伸法以两种聚丙烯为原料制备微孔膜.通过考察原料分子量数据发现高分子量聚丙烯(PPH)在高分子量级分(重均分子量>106)含量上大于低分子量聚丙烯(F401).PPH的弛豫时间在相同条件下也远大于F401.红外二向光法结果表明,PPH在相同熔体牵伸比下片晶取向度较F401高.相同加工条件下PPH微孔膜片较F401成孔分布更均匀,孔径尺寸也更均匀.2种微孔膜孔隙率都随熔体牵伸比的增加而提高,微孔分布随着熔体牵伸比的提高和片晶取向度的增加而趋于均匀,孔尺寸也随之区域均匀.研究表明,聚合物树脂中高分子量级分含量是影响预制膜中片晶取向度、冷热拉伸成孔分布和尺寸均匀度的重要影响因素.     

Morphology and Mechanical Properties of Palm Based Fly Ash Reinforced Dynamically Vulcanized Natural Rubber/Polypropylene Blends

Palm based fly ash (PFA) is a solid waste of palm oil processing industry which contains silica components. These components are typically used to improve the mechanical properties of rubber-based products. This research aims to study the effect of the PFA as a filler on the morphology and properties of thermoplastic vulcanizate (TPV) based on a mixture of natural rubber (NR) and polypropylene (PP). TPV samples were prepared using the internal mixer at a mass ratio of NR/PP 70/30. Maleated polypropylene (MA-g-PP) 5% mass was added as a compatibilizer, filler content was varied from 15 to 45 per hundred rubber (phr). Paraffin and palm oil were added as a plasticizer with contents of 5 to 50 phr. Other additives include ZnO 5 phr, stearic acid 2 phr, trimethylquinone 1 phr, mercaptodibenzo-thiozyldisulfide 0.6 phr and 3 phr sulfur. The results showed that the use of PFA provides good tensile strength properties, a relatively homogeneous morphology, and low water absorption rate. The use of paraffin plasticizer produces a higher tensile strength compared to palm oil, but the elongation at break which produced the contrary. The best morphology and tensile properties of TPV (NR/PP 70/30) are on PFA and paraffin contents of 30 phr and 25 phr, respectively.     

Preparation and physical properties of poly(trimethylene terephthalate)/metallocene isotactic polypropylene conjugated fibers

Poly(trimethylene terephthalate) (PTT) and metallocene isotactic polypropylene (MIPP) polymers were extruded (in the proportions of 75/25, 50/50, 25/75) from two melt twin-screw extruders to prepare three PTT/MIPP conjugated fibers. This study investigated the preparation and physical properties of PTT/MIPP conjugated fibers using gel permeation chromatograph (GPC), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), potentiometer, a rheometer, the density gradient, wide-angle X-ray diffraction (WAXD), extension stress-strain measurement and scanning electron microscope (SEM). Melting behavior of PTT/MIPP polyblended polymers exhibited negative-deviation blends (NDB) and the 50/50 blend of PTT/MIPP showed a minimum value of the melt viscosity. Experimental results of the DSC indicated PTT and MIPP molecules formed immiscible system. The tenacity of PTT/MIPP conjugated fibers decreased initially and then increased as the MIPP content increased. Crystallinities and densities of PTT/MIPP conjugated fibers were the linear relation with the blend ratio. PTT and MIPP polymers were proved to be an incompatible system. On the morphological observation, it was revealed that the blends were in a dispersed phase structure. The pore/fiber morphology of a larger size from 0.5 to 3 μm in diameter was observed after 1,1,1,3,3,3-hexafluoro-2-propanol (PTT was removed)/paraffin oil (MIPP was removed) treatment on the cross-section of PTT/MIPP conjugated fiber. In this paper, PTT micro fibers were produced successfully.     

分子量分布对等规聚丙烯卷绕丝织构形成的影响

本文研究了分子量分布对聚丙烯卷绕丝结构和性能的影响。结果表明,聚丙烯树脂中的高分子量尾端对卷绕丝的结构有明显影响。在通常的纺丝条件下,用控制降解的聚丙烯树脂纺得的卷绕丝具有低取向的次晶结构;而在相同的粘均分子量和纺丝条件下,高分子量尾端的存在使聚丙烯易于在纺丝线上生成结晶性较高的α-晶型,卷绕丝的取向也随高分子量尾端而显著增大。高分子量尾端对卷绕丝结构的影响,导致卷绕丝牵伸性能和成品纤维力学性能变差。     

SAXS experiments on gel-spun polyethylene fibers

The properties of gel-spun polyethylene fibers hot-drawn to the maximum draw ratio depend on the spinning conditions. Different spinning conditions result in two types of structure in the paraffin oil containing fibers: an isotropic lamellar structure or a shish-kebab structure. Meridional SAXS experiments can identify the structure present. After extraction, these structures are still present but can be detected only in a more indirect way by SAXS experiments because of an excessive contribution of void scattering. During hot-drawing both structures are transformed into a more fibrillar structure. The shish-kebab structures can be drawn only to relatively low hot-draw ratios with an incomplete transformation of the lamellar overgrowth into the fibrils, as demonstrated by the presence of a meridional SAXS maximum/shoulder. This leads to relatively weak fibers. Lamellar structures can be drawn to high draw ratios by chain unfolding. A nearly complete transformation of the lamellae into fibrils is obtained and the fibers have excellent properties. The information about the morphology obtained by SAXS, DSC, WAXS, and SEM can be used to establish a relation between morphology and properties.     

Attachment of nickel oxide nanoparticles on the surface of palygorskite nanofibers

To study the relationship between emulsion stability and polymer emulsifier concentration, the preparation of paraffin oil emulsions by hydroxypropyl methylcellulose (HPMC) was carried out with HPMC concentrations below the overlapping concentration (C(*)) of HPMC. The stability of the emulsions incorporating HPMC was investigated by measuring the creaming velocity, volume fraction of emulsified paraffin oil, oil droplet size, and some rheological responses such as the stress-strain sweep curve and strain and frequency dependences of dynamic viscoelastic moduli. The paraffin oil was almost emulsified by HPMC above C(*)/20: the volume fraction of paraffin oil in the emulsion was higher than 0.72. Increasing in the HPMC concentration led to decreases in both the average oil droplet size and creaming velocity and an increase in the yield stress. All emulsions behaved as solid-like viscoelastic matter. Additionally, the measured dynamic storage moduli were compared with those calculated from a relationship based on functions of the volume fraction of oil in the emulsions and Laplace pressure; good agreement between the measured and calculated moduli was obtained. On the other hand, at HPMC concentrations below C(*)/50, the emulsified paraffin oil became unstable and the oil and the HPMC solution eventually separated.     

涂石蜡大米傅立叶变换红外吸收光谱识别分析

针对11种未涂石蜡大米和18个涂不同量石蜡的大米样品,以石油醚提取的油脂为试样,采用傅立叶变换红外光谱仪,扫描样品的傅立叶变换红外吸收光谱,并对光谱进行预处理,提取红外特征信息,将2855与1746、1462与1163 cm-1处特征峰的面积比值为坐标,采用Origín 6.0软件作识别分类图.结果表明:特征峰的面积比值与所涂石蜡量成线性变化,大米油脂的特征峰面积比值在一定的区域分布,涂以0.05%以上石蜡的大米,其油脂特征峰面积比值与未涂石蜡米油脂的值有一定区别.     

On some relations between advancing, receding and Young's contact angles

Problems of experimental determination and theoretical verification of equilibrium contact angles are discussed basing on the literature data. A relationship between the advancing and receding contact angles versus the equilibrium contact angle is described and then verified using the literature contact angles determined on paraffin wax and polypropylene. Using the proposed relationship and experimentally determined equilibrium contact angles, obtained by plotting the advancing and receding contact angles versus the contact angle hysteresis or by applying vibration of the system liquid drop/solid surface, it is found that the same value of the surface free energy for paraffin wax is calculated from the contact angles of water and ethylene glycol. However, in the case of polypropylene some inconsistency appears between the equilibrium contact angles of the probe liquid used and the calculated surface free energy. More experimental data of the equilibrium contact angle are needed to verify further the relationship.     

Monitoring the polymerization process of polypyrrole films by thermogravimetric and X-ray analysis

Bio-composite fibers were developed from wood pulp and polypropylene (PP) by an extrusion process. The thermo-physical and mechanical properties of wood pulp-PP composite fibers, neat PP and wood pulp were studied using thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and dynamic mechanical analysis (DMA). The thermal stability of bio-composite fibers was found to be significantly higher than pure wood pulp. An understanding into the melting behaviour of the composite system was obtained which would assist in selecting a suitable temperature profile for the extruder during processing. The visco-elastic properties of bio-composite fibers were also revealed from the study. The generated bio-composite fibers were also characterized using Fourier transform infrared spectroscopy (FTIR) to understand the nature of chemical interaction between wood pulp reinforcement and PP matrix. The use of maleated polypropylene (MAPP) as a compatibilizer was investigated in relation to the fiber microstructure. Changes in absorption peaks were observed in FTIR spectra of bio-composite fibers as compared to the pure wood pulp which indicated possible chemical linkages between the fiber and polymer matrix.     

Polypropylene as a potential matrix for the creation of shape stabilized phase change materials

Phase change materials, based on isotactic polypropylene (PP) blended with soft and hard Fischer−Tropsch paraffin wax respectively, were studied in this paper. DSC, DMA, TGA and SEM were used to determine the structure and properties of the blends. While paraffin waxes in the blend changed state from solid to liquid, the PP matrix kept the material in a compact shape. Strong phase separation was observed in both cases, which was more pronounced in the case of soft paraffin wax. Despite the fact that both grades of paraffin wax are not miscible with PP due to different crystalline structures, it was shown that the hard Fischer−Tropsch paraffin wax is more compatible with PP than the soft one. Both waxes plasticized the PP matrix. TGA showed that PP blended with the hard Fischer−Tropsch wax degrades in just one step, whereas blends containing soft paraffin wax degrade in two distinguishable steps. SEM exposed a completely different morphology for the two paraffin waxes and confirmed the lower compatibility of PP and soft paraffin wax. The soft and hard characters of the waxes were manifested in the viscoelastic properties, where the blends containing soft paraffin wax exhibited a lower elastic modulus than pure polypropylene, whereas the hard Fisher−Tropsch paraffin wax solidified the matrix. However, both kinds of blends were able to sustain the dynamic forces applied by the DMA within five cycle runs implying good shape stability.     

Transfer of load from matrix to fiber in self-reinforced polymer composites

The tensile properties of self-reinforced polypropylene composites, obtained by rapid extension of an isotactic polypropylene/atactic polypropylene melt, have been measured and correlated to morphological parameters derived from x-ray experiments. The longitudinal morphology of the core-fibrils is found to be independent of sample composition, while the lateral thickness of the fibers varies between 220 Å for iPP and 110 Å for the blend containing 50 wt.% aPP. Critical fiber lengths, as a function of sample composition and the elastic modulus and the yield stress of the fibers, could be determined. While the number of corefibrils increases with mass fraction of atactic polypropylene, the length of the lateral interface between fiber and matrix and the interface volume decreases with increasing aPP mass fraction. It is shown that this interface is responsible for the mechanical behavior of the composite by effecting the transfer of load from matrix to fiber.